KR20120075496A - Compositions containing fluorine substituted olefins - Google Patents

Abstract

The use of tetrafluoropropene, especially for the cooling installation of (HFO-1234), is described for various uses. These materials are generally used as heating and cooling refrigerants, blowing agents, aerosol propellants, solvent compositions and fire extinguishing and suppressing agents.

Description

Composition containing fluorine substituted olefins {Compositions Containing Fluorine Substituted Olefins}

The present invention relates in particular to compositions for use in various applications, including cooling systems, and to methods and systems of using the compositions. In a more preferred aspect, the present invention relates to a refrigerant composition comprising at least one multi fluorinated olefin of the present invention.

Fluorocarbon-based fluids are known to be used in a wide variety of applications, primarily for commercial and industrial applications. For example, fluorocarbon based fluids are frequently used as effective fluids in systems such as for air conditioning, heat pumps and cooling. Vapor compression cycles are one of the most commonly used types of methods for performing cooling or heating in cooling systems. The vapor compression cycle typically absorbs heat at relatively low pressure and then releases heat from the liquid to the vapor phase, then releases heat at a relatively low pressure and temperature, compresses the vapor to a relatively increased pressure, and Condensing the vapor into the liquid to release heat at increased pressure and temperature, and then reducing the pressure to resume phase change of the refrigerant.

While the first purpose of cooling is to release heat from objects or other fluids at relatively low temperatures, the first purpose of heat pumps is to apply heat at temperatures higher than ambient.

Some fluorocarbons have been suitable components for many years for many applications, among many heat exchange fluids such as refrigerants. For example, fluoroalkanes such as fluoroalkanes, chlorofluoromethane and chlorofluoroethane derivatives have been used extensively as refrigerants, including air conditioning and heat pump applications because of their unique combination of chemical and physical properties. Most of the refrigerants commonly used in vapor compression systems are single component fluids or azeotropic mixtures.

In recent years, there has been increasing interest in the potential hazards to the Earth's atmosphere and climate, and some chlorine-based components have been found to be particularly problematic in this regard. The use of chlorine-containing compositions (chlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCF), etc.) as refrigerants in air-conditioning and cooling systems is regulated for use due to the ozone-depleting properties associated with most of these compounds. have. Therefore, there is an increasing demand for new fluorocarbon and hydrocarbon compounds and compositions that will provide alternatives for cooling and heat pumps. For example, there is a need to retrofit chlorine-containing cooling systems by replacing chlorine-containing refrigerants with non-chlorine-containing refrigerant components that do not destroy the ozone layer, such as hydrofluorocarbons (HFCs).

However, it is important to note that, in general, potential alternative refrigerants must also have such properties in many respects as the most widely used fluids such as good heat transfer properties, chemical stability, low or non-toxicity, non-flammability and lubrication compatibility with others. .

Applicants have recognized that lubrication compatibility is particularly important in many applications. Furthermore, it is highly desirable that the cooling fluid be compatible with the lubricants used in the compressor units used in most cooling systems. Unfortunately, many non-chlorine-containing cooling fluids, including HFCs, are relatively relative to CFCs and HFCs in traditionally used lubricant types, including, for example, mineral oils, alkylbenzenes or poly (alpha-olefins). Insoluble and / or not mixed. In order for the cooling fluid-lubricant combination to function effectively at a suitable level in compression cooling, air conditioning and / or heat pump systems, the lubricant must be sufficiently soluble in the cooling solution over a wide operating temperature range. Such solubility lowers the viscosity of the lubricant and makes it easier to flow throughout the system. Without such solubility, lubricants tend to stay in the coils of the evaporator of cooling, air-conditioning or heat pump systems, as well as other parts of the system, thus reducing the effectiveness of the system.

With regard to efficacy in use, it is important to recognize that the reduction in thermodynamic efficiency or energy efficiency of refrigerants can lead to an increased environmental impact of increased fossil fuel use due to increased demand for electrical energy.

It is also generally believed that CFC refrigerant substitutes are effective without the engineering changes to traditional vapor compression techniques that typically use CFC refrigerants.

Flammability is another important property in many applications. That is, it is believed that the use of non-combustible compositions is important or essential for many applications, especially for thermal transfer applications. Therefore, it is often advantageous to use non-combustible compounds in such compositions. As used herein, the term "non-flammable" refers to a compound or composition that has been determined to be non-flammable, as defined in accordance with the 2002 ASTM Standard E-681 described herein. Unfortunately many other HFCs suitable for use in refrigerant compositions are not nonflammable. For example, fluoroalkane difluoroethane (HFC-152a) and fluoroalkene 1,1,1-trifluoropropene (HFO-1243zf) are each flammable and therefore not suitable for use in many applications. .

Higher fluoroalkenes, fluorine-substituted alkenes having at least 5 carbon atoms, have been proposed for refrigerants. US Pat. No. 4,788,352-Smutny relates to a process for the preparation of fluorinated C ₅ -C ₈ compounds having at least some degree of unsaturation. The Smutny patent relates to such higher olefins known to have applications as refrigerants, insect repellents, dielectric fluids, heat transfer fluids, solvents and intermediates in various chemical reactions (see columns 1, lines 11-22).

The fluorinated olefins described in Smutny have some efficacy in heat transfer applications, but these compounds also have other disadvantages. For example, some of these compounds tend to attack articles such as plastics, such as acrylic resins and ABS resins, which are used in particular general applications. Furthermore, the higher olefin compounds described in Smutny may also be unsuitable for some uses because of the potential toxicity of such compounds that may result as a result of the antiparasitic activity described in Smutny. In addition, such compounds have a boiling point that is too high for useful use as a refrigerant in some applications.

Bromofluoromethane and bromochlorofluoromethane derivatives, especially bromotrifluoromethane (Halon 1301) and bromochlorodifluoromethane (Halon 1211), are used in airplane cabins and computer rooms. It has been widely used as a fire extinguishing agent in the same enclosed space. However, the use of various halons has changed due to high ozone depletion. Moreover, since halons are often used in areas where humans exist, suitable alternatives should be safe for humans at the concentrations necessary to suppress or extinguish fire.

Applicants are therefore potentially useful for a myriad of applications, including vapor compression heating and cooling systems and methods, while compositions, in particular heat transfer compositions, fire extinguishing / inhibiting compositions, foaming agents, which can avoid one or more of the aforementioned disadvantages, It has been recognized the need for solvent compositions and compatibilizers.

Applicants claim that the above and other needs are one or more C3 or C4 fluoroalkenes, more preferably compounds having the formula:

It can be satisfied by a compound comprising a.

Provided that X is a C ₂ or C ₃ unsaturated, substituted or unsubstituted alkyl radical, each R is independently Cl, F, Br, I or H, and z is 1-3. More preferred among the compounds of formula I are the cis- and trans-isomers of 1,3,3,3-tetrafluoropropene (HFO-1234ze).

The present invention also provides a method and system using the composition of the present invention, wherein the method and system comprise heat transfer, foaming, solvation, flavor and fragrance extraction and dissipation, and aerosol Methods and systems for generation.

1 shows the density of foam produced according to an embodiment of the invention.

Composition

The present invention relates to a composition comprising at least one 3-4 carbon atoms, more preferably three carbon atoms and at least one carbon-carbon double bond. When the fluoroalkene compound of the present invention contains at least one hydrogen, it is simply referred to herein as hydrofluoro-olefin or "HFO". Although it is contemplated that the currently mentioned HFO may comprise two carbon-carbon double bonds, such compounds are not considered to be preferred here.

As noted above, the composition comprises one or more compounds according to formula I. In a more preferred embodiment, the composition comprises a compound of formula II:

Wherein each R is independently Cl, F, Br, I or H,

R 'is (CR ₂ ) _n Y,

Y is CRF ₂ ,

And n is 0 or 1.

In a very preferred embodiment, Y is CF ₃ , n is 0 and at least one of the remaining R is F.

Applicants generally believe that compounds of formulas (I) and (II) specified above are generally effective and have utility as refrigerant compositions, blowing agent compositions, compatibilizers, aerosols, propellants, fragrances, flavor blends, and solvent compositions of the present invention. Applicants, however, have surprisingly and unexpectedly found that a composition having a structure consistent with the above formula has a very preferably low level of toxicity compared to the other of such compounds. The present findings have potentially myriad advantages and benefits, not only for refrigerant compositions, but also for combinations of refrigerant compositions that meet the above-mentioned formulas, as well as all other compositions, or else relatively toxic compounds that satisfy the above formulas. It's easy to think of it. More particularly Applicants believe that a relatively low degree of toxicity is associated with the compound of formula II, more preferably Y is CF ₃ , at least one R is H in the unsaturated terminal carbon and at least one of the remaining R is F do. Applicants also believe that the structural, geometric, stereoisomers of such compounds are effective and beneficially low toxicity.

In a very preferred embodiment, in particular in particular embodiments which are low toxicity compounds, n is zero. In a particularly more preferred embodiment, the composition of the present invention comprises one or more tetrafluoropropenes. The term "HFO-1234" is used herein to refer to all tetrafluoropropenes. Among the tetrafluoropropenes, cis- and trans-1,3,3,3-tetrafluoropropene (HFO-1234ze) are more preferable. The term "HFO-1234ze" is used herein to generally refer to 1,3,3,3-tetrafluoropropene, whether in cis- and trans-forms. The above "cis-HFO-1234ze" and "trans-HFO-1234ze" are used herein to describe the cis- and trans-forms of 1,3,3,3-tetrafluoropropene, respectively. Therefore, "HFO-1234ze" is within the scope and includes cisHFO-1234ze, transHFO-1234ze and all combinations and mixtures thereof.

Although the properties of cisHFO1234ze and transHFOze differ in at least some respects, it is contemplated that each of these mixtures, alone or in combination with other compounds, is suitable for use in the uses, methods and systems described herein. For example, transHFO-1234ze may be more desirable for use in certain cooling systems because of its relatively low boiling point (-19 ° C.), nevertheless cisHFO-1234ze, which has a boiling point of + 9 ° C., may also be used in the present invention. Practical in certain cooling systems. Thus, it will be understood that "HFO-1234ze" and 1,3,3,3-tetrafluoropropene refer to both stereoisomers, and the use of this term means that each of the cis- and trans-forms is expressed differently. If not, it is used for this purpose or with the intention of indicating useful.

HFO-1234 compounds are known materials and are described in Chemical Abstracts databases. The preparation of fluoropropenes such as CF ₃ CH═CH _{2 by} catalytic vapor phase fluorination of various saturated and unsaturated halogen-containing C ₃ compounds is described in US Pat. No. 2,889,379; 4,798,818, each of which is incorporated in document EP974,571. EP974,571, also incorporated herein by reference, discloses 1,1,1, in the liquid phase with chromium-based catalysts at elevated temperatures or in the liquid phase with alcohol solvents of KOH, NaOH, Ca (OH) ₂ or Mg (OH) ₂ A method for preparing 1,1,1,3-tetrafluoropropene is disclosed by contacting 3,3-pentafluoropropane (HFC-245fa). Methods for preparing compounds such as the present invention are also described in US Patent Application Attorney docket number (H0003789 (26267)), generally entitled "Method for preparing fluoropropenes" It is described in.

The composition, in particular the composition comprising HFO-1234ze, has beneficial properties for many important reasons. For example, Applicants note that based on at least some mathematical modeling, the fluoroolefins of the present invention have substantially no negative impact on atmospheric chemistry and can neglect the contribution to ozone destruction compared to some halogenated species. . Therefore, more preferred compositions of the present invention also do not contribute substantially to global warming compared to many currently used hydrofluoroalkanes.

In a particularly preferred form, the compositions of the present invention have a Global Warming Potential (GWP) of about 1000 or less, more preferably 500 or less and even more preferably 150 or less. In certain embodiments, the GWP of the composition is about 100 or less, more preferably 75 or less. "GWP" as used herein, as defined in the literature, "2002, Scientific Measurements of Ozone Depletion, Global Ozone Report and Monitoring Project of the World Meteorological Association," was measured for carbon dioxide over 100 years.

As a particularly preferred form, the composition also preferably has an ozone depletion index (ODP) of 0.05 or less, more preferably 0.02 or less, even more preferably almost zero. "ODP" is defined here as a citation, as defined in "2002, Scientific Measurements of Ozone Depletion, the World Meteorological Association's Global Ozone Reporting and Monitoring Project".

The content of a compound of formula I, in particular HFO-1234, included in the composition may vary widely depending on the particular application, and compositions comprising more than trace and up to 100% of the compound are within the scope of the present invention. Belongs to. Furthermore, the compositions of the present invention may be azeotropic, azeotropic-like, or non-azeotropic. In a more preferred embodiment, the composition comprises from about 5% to about 99%, more preferably from about 5% to about 95% by weight of HFO-1234, preferably HFO-1234ze. Many additional compounds can be included in the present compositions, and the presence of all such compounds is included within the scope of the present invention. As a particularly preferred embodiment, the composition may comprise one or more of the following in addition to HFO-1234ze;

Difluoromethane (HFC-32)

Pentafluoroethane (HFC-125)

1,1,2,2-tetrafluoroethane (HFC-134)

1,1,1,2-tetrafluoroethane (HFC134a)

Difluoroethane (HFC-152a)

1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea)

1,1,1,3,3,3-hexafluoropropane (HFC-236fa)

1,1,1,3,3-pentafluoropropane (HFC-245fa)

1,1,1,3,3-pentafluorobutane (HFC-365mfc)

water

CO ₂

Additional components that may be included in the composition, as well as the relative amounts in the components, may vary widely within the broad general scope of the invention, depending on the particular use of the composition, and all these relative amounts are within the scope of the invention. .

Heat transfer composition

Although it is anticipated that the compositions of the present invention may comprise the compounds of the present invention in a wide range of amounts, generally the refrigerant compositions of the present invention are in accordance with formula (I), more preferably compound (s) according to formula (II). And, more preferably, HFO-1234ze in an amount of at least about 50%, more preferably at least about 70% by weight of the composition. In many embodiments, the heat transfer composition of the present invention preferably comprises transHFO-1234ze. In certain preferred embodiments, the heat transfer composition of the present invention has a cis of about 1:99 to 10:99, more preferably about 1:99 to 5:95, and more preferably about 1:99 to 3:97: Trans weight ratios include a mixture of cisHFO-1234ze and transHFO1234ze.

The compositions of the present invention may include other components for the purpose of enhancing or providing certain functionality in the composition or in some cases to reduce the cost of the composition. For example, refrigerant compositions according to the invention, in particular refrigerant compositions used in vapor compression systems, generally comprise lubricant in an amount of about 30-50% by weight of the composition. In addition, the composition of the present invention may include affinity agents such as propane for the purpose of assisting the miscibility and / or solubility of the lubricant. Such affinity agents including propane, butane and pentane are preferably present in amounts of about 0.5-5% by weight of the composition. Mixtures of surfactants and solubilizers as disclosed in US Pat. No. 6,516,837 may also be added to the compositions of the present invention to assist in oil solubility. Polyol esters (POEs) and polyalkylene glycols (PAGs), silicone oils, mineral oils, alkyl benzenes (ABs) and poly (alpha-olefins) (PAO) used in chillers with hydrofluorocarbon (HFC) refrigerants; Such commonly used cooling lubricants may be used with the refrigerant compositions of the present invention.

Many present cooling systems are adapted for use with the presently present refrigerants, and the compositions of the present invention are believed to be adaptable for use in many such systems with or without system modifications. In many applications the compositions of the present invention may provide an advantage as a substitute in systems based on refrigerants that currently have relatively high capacity. Furthermore, in implementations where it is necessary to use the lower capacity refrigerant compositions of the present invention, for example to replace higher capacity refrigerants at a cost, such an implementation of the present invention offers potential advantages. Thus, in certain embodiments, it is desirable to use the compositions of the present invention as a replacement for existing refrigerants such as HFC-134a, and in particular to use compositions that comprise a substantial portion of transHFO-1234ze, and in some embodiments Preference is given to using a composition consisting essentially of transHFO-1234ze. In certain applications, the refrigerants of the present invention allow for the advantageous use of potentially larger displacement compressors, thus having better energy efficiency than other refrigerants such as HFC-134a. The refrigerant compositions of the present invention, in particular compositions comprising transHFP-1234ze, thus offer the possibility of achieving competitive advantages on an energy basis for refrigerant replacement applications.

Compositions of the present invention, in particular comprising compositions comprising HFO-1234ze, are also typically used in cooling devices used with commercial air conditioning systems (when used in original systems or as substitutes for refrigerants such as R-12 and R-500). Has an advantage. In this particular embodiment, it is preferred to include about 0.5-5% of a flame retardant such as CF3l in the HFO-1234ze composition present.

The methods, systems and compositions of the present invention are thus adaptable for use with automated air conditioning systems and devices, commercial refrigerant systems and devices, chillers, residential refrigerators and freezers, general air conditioning systems, heat pumps, and the like.

Blowing agent, foam ( foam ) And foamable compositions

In addition, the blowing agent comprises or comprises one or more of the present compositions. As above, the compositions of the present invention may comprise the compounds of the present invention in a wide range of amounts. However, as a preferred composition for use as blowing agent in connection with the present invention, the compounds according to formula (I) and even more preferably formula (II) are present in an amount of at least 5% by weight, more preferably about 15% by weight It is generally preferred to be present in amount. In certain preferred embodiments, the blowing agent compositions of the present invention comprise in addition to HFO-1234 (preferably HFO-1234ze) a co-foaming agent, filler, vapor compression modifier, or one or more of the following components for other purposes. :

Difluoromethane (HFC-32)

Pentafluoroethane (HFC-125)

1,1,2,2-tetrafluoroethane (HFC-134)

1,1,1,2-tetrafluoroethane (HFC-134a)

Difluoroethane (HFC-152a)

1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea)

1,1,1,3,3,3-hexafluoropropane (HFC-236fa)

1,1,1,3,3-pentafluoropropane (HFC-245fa)

1,1,1,3,3-pentafluorobutane (HFC-365mfc)

water

CO ₂

It is anticipated that the blowing agent composition of the present invention may comprise cisHFO-1234ze, transHFO1234ze or mixtures thereof. In certain preferred embodiments, the blowing agent compositions of the present invention comprise a mixture of cisHFO-1234ze and transHFO1234ze in a cis: trans weight ratio of about 1:99 to 10:99, more preferably about 1:99 to 5:95.

In another embodiment, the present invention provides foamable compositions prepared using the compositions of the present invention, more preferably polyurethanes, polyisocyanurates and extruded thermoplastic foam compositions. As such foam embodiments, one or more of the compositions are included in the foamable composition as a blowing agent or as part thereof, and the composition is preferably known in the art under suitable conditions for forming a foam or cellular structure. One or more additional components capable of reacting and / or foaming. The present invention also relates to foams, preferably constant cell foams, prepared from polymer foam formulations containing blowing agents comprising the compositions of the invention. In another embodiment, the present invention provides a foamable composition comprising a thermoplastic or polyolefin foam, such as polystyrene (PS), polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) foams, preferably low density foams. to provide.

In certain preferred embodiments, dispersants, cell stabilizers, surfactants and other additives may be mixed into the blowing agent compositions of the present invention. Although optional, it is preferably added as a surfactant to serve as a cell stabilizer. Several representative materials are sold under the names DC-193, B-8404 and L-5340, which are hereby incorporated by reference, generally polysiloxane poly, as disclosed in US Pat. Nos. 2,834,748, 2,917,480 and 2,846,458. Oxyalkylene block co-polymers. Other optional additives of the blowing agent mixture include tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate, tri (2,3-dibromopropyl) -phosphate, tri (1,3-dichloropropyl) phosphate, Flame retardants such as diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.

Propellant and Aerosol Compositions

In another aspect, the present invention essentially provides a propellant composition comprising or comprising the composition of the present invention, which propellant composition is preferably a sprayable composition. The propellant composition of the present invention preferably comprises a sprayable material and a propellant comprising, consisting essentially of or consisting of the composition according to the invention. Inert components, solvents, and other materials may also be present in the sprayable mixture. Preferably the sprayable composition is an aerosol. Materials suitable for nebulization include, but are not limited to, cosmetic materials such as deodorants, perfumes, hairsprays, cleansers, and varnishes, as well as medical materials such as anti-asthmatic, anti-drug drugs. A medicament or other therapeutic agent is preferably present in the composition in a therapeutic amount in the substantial remainder of the composition comprising a compound of formula I of the present invention, preferably HFO-1234, and more preferably HFO-1234ze.

Industrial, consumer or medicinal aerosol products typically contain one or more propellants, together with one or more active ingredients, inert ingredients or solvents. The propellant provides the force to discharge the product in aerosol form. Some aerosol products are propelled by compressed gases such as carbon dioxide, nitrogen, nitrogen monoxide and even air, while most commercial aerosols use liquefied gas propellants. The most commercially used liquefied gas propellants are hydrocarbons such as butane, isobutane, and propane. Dimethyl ether and HFC-1521 (1,1-difluoroethane) are also used, alone or in combination with a hydrocarbon propellant. Unfortunately, all these liquefied gas propellants are quite flammable and their integration into aerosol formulations often forms flammable aerosol products.

Applicants have recognized the continuing need for non-flammable, liquefied gas propellants used to make aerosol products. The present invention particularly and preferably comprises the compositions of the invention for use in certain industrial aerosol products, including, for example, spray cleaners, lubricants, and the like, in medicinal aerosols, for example, in the delivery of medicaments to the lungs or mucous membranes. HFO-1234, and more preferably a composition comprising HFO-1234ze. Examples thereof include metered dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for transport of medication into accessible mucosal or nasal passages. The invention also includes a method of treating the discomfort, disease and similar health related problems of an organism (human or animal) comprising applying a composition of the invention containing a medicament or other therapeutic ingredient to an organism in need of treatment. do. In certain preferred embodiments, applying the composition of the invention comprises providing an MDI containing the composition of the invention (e.g., introducing the composition into the MDI), and then draining the composition of the invention from the MDI. It involves doing.

Compositions of the present invention, particularly those comprising or consisting essentially of HFO-1234ze, can provide non-combustible, liquefied gas propellants and aerosols that do not substantially contribute to global warming. The compositions of the present invention can be used to prepare a variety of industrial aerosols or other sprayable compositions, such as contact cleaners, dusters, lubricant sprays, and the like, and consumer aerosols, such as personal care products, housewares, and automotive products. HFO-1234ze is particularly preferred for use as an important component of propellant compositions in medical aerosols such as metered dose inhalers. In many applications the medical aerosols and / or propellants and / or nebulizable compositions of the present invention are in addition to the compounds of formula (I) or (II) (preferably HFO-1234ze), beta-antagonists, corticosteroids or other Medicaments such as medicaments, and optionally other ingredients such as surfactants, solvents, other propellants, fragrances and other excipients. The compositions of the present invention, unlike many of the compositions previously used for such applications, have excellent environmental properties and are not considered as potential contributors to global warming. The compositions of the present invention thus provide, in certain preferred embodiments, substantially non-flammable, liquefied gas propellants with very low global warming potentials.

Air fresheners and spices

The compositions of the present invention also provide advantages when used as part of and as carriers for flavor blends and fragrance blends. The suitability of this composition for this purpose is evidenced by the test method in which 0.39 grams of Jasmon is placed in a heavy wall glass tube. 1.73 grams of R-1234ze was added to the glass tube. The tube was then frozen and sealed. Upon thawing of the tube, the mixture was found to have one liquid phase. The solution contained 20% by weight of Jasmon and 80% by weight of R-1234ze, thus establishing favorable use as a carrier or part of a delivery system for flavor blends in aerosols and other formulations. It also established the potential as an extractant for fragrances, including plants.

Method and system

The compositions of the present invention are useful in connection with a variety of methods and systems, including heat transfer fluids in methods and systems for heat transfer, such as cooling, air conditioning, and heat pump systems. The compositions are also advantageous for use in aerosol generating systems and methods, and preferably comprise or comprise an aerosol propellant in such systems and methods. Methods of forming foam and methods of extinguishing and suppressing fire are also included in one aspect of the present invention. The present invention also provides, in one aspect, a method for removing residue from an article in which the composition is used as a solvent composition in such methods and systems.

Heat transfer method

Preferred methods of heat transfer generally include providing a composition of the present invention and wherein heat transferred to or from the composition causes a phase change of the composition. For example, the method provides for absorbing heat from a fluid or article, and more preferably evaporating the cooled refrigerant composition cooled near the body or fluid to produce and cool the vapor comprising the composition. Preferably the method further comprises compressing the refrigerant vapor which produces the vapor of the composition at a relatively increased pressure, usually using a condenser or similar device. Generally, the step of compressing the steam causes a supply of heat to the steam and therefore a relatively high temperature of the high pressure steam. Preferably the method comprises removing from this relatively high temperature, high pressure steam at least a portion of the heat increased by the evaporation and condensation steps. The heat removal step preferably includes condensing the hot, high pressure steam while the steam is in a high pressure condition to produce a relatively high pressure liquid comprising the composition of the present invention. This relative high pressure liquid is then preferably nominally isenthalpic reduced at a pressure which produces a relatively low temperature low pressure liquid. In this embodiment, this cooled temperature cooled liquid is then cooled by heat transfer from the body or fluid.

As another method embodiment of the present invention, the composition of the present invention may be used in a method of carrying out heating comprising refrigerant condensation comprising a heated composition near a liquid or body. As mentioned above, this method is often reverse circulation for the cooling cycle.

Foaming method

One embodiment of the present invention relates to a method of forming a foam, more preferably to a polyurethane and a polyisocyanurate foam. As is known in the art, the process generally comprises the steps of providing a foaming agent composition of the invention, adding (directly or indirectly) a foaming agent composition to the foaming composition and reacting the foaming composition under effective conditions to form a foam or cellular structure. Forming a step. One type of method known in the art is the foam implementation of the present invention, as described in New York, NY, John Willie & Sons, 1962, Sanders and Frisch, Volumes I and II, "Polyurethane Chemistry and Technology," cited herein. It can be used or applied for In general, these preferred methods combine isocyanurates, polyols or mixtures of polyols, one or more blowing agents or blowing agent mixtures of the composition and other materials such as catalysts, surfactants and optionally flame inhibitors, pigments, or other additives. Polyurethane or polyisocyanurate foam production.

In many applications it is convenient to provide the polyurethane or polyisocyanurate foam component as a pre-mix preparation. The isocyanates and optionally surfactants and blowing agents comprise the first component, usually referred to as the "A" component. Such polyols or polyol mixtures, surfactants, catalysts, blowing agents, flame suppressors, and other isocyanate-reactive components include a second component, commonly referred to as the "B" component. Thus polyurethane or polyisocyanurate foams are prepared by introducing each of the A and B side components in advance together by hand mixing and preferably by mechanical mixing techniques for the production of small quantities, and by means of blocks, steps, Laminates, pour-in-place and other items, spray applied foams, foams and the like. Optionally, other ingredients such as flame retardants, pigments, auxiliary blowing agents, and other polyols may be added to the mixing head or reaction site as a third air stream. But most preferably all of them are included in said one B-component.

Thermoplastic foams can also be prepared using the compositions of the present invention. For example, conventional polystyrene and polyethylene formulations can be combined with the composition in conventional manner to produce rigid foams.

How to wash

The invention also provides a method of applying the composition of the invention to an article to remove contaminants from an article, part, part, substrate, or any other article or portion thereof. For convenience, the term "article" as used herein refers to all such articles, parts, parts, substrates, etc., which is further intended to refer to any surface or portion thereof. The term "contaminant" as used herein also means any unwanted material or material present in the article, even if such material is intentionally placed in the article. For example, in the manufacture of semiconductor devices, it is common to deposit a photocurable material on a substrate to form a mask for an etching operation and then remove the photocurable material from the substrate. The term "contaminant" as used herein is intended to cover or surround such photocurable material.

Preferred methods of the present invention include applying the present composition to an article. Although numerous and various cleaning techniques are contemplated for use of the compositions of the present invention, it is contemplated that the present invention will be particularly useful for use in combination with supercritical cleaning techniques. Supercritical cleaning is shown in US Pat. No. 6,589,355, which is assigned to the assignee of the present invention and is hereby incorporated by reference. For supercritical cleaning applications, the present cleaning compositions, further one or more additional compositions such as HFO-1234 (preferably HFO-1234ze), CO ₂ and other known in connection with use in combination with supercritical cleaning applications Certain implementations comprising additional compositions are preferred. Any implementation for using the cleaning compositions of the present invention in combination with certain vapor degreasing and solvent cleaning methods is also possible and required.

How to reduce flammability

According to certain other preferred embodiments, the present invention provides a method for reducing the flammability of a fluid, the method comprising adding a compound or composition of the present invention to the fluid. Flammability associated with any of a wide variety of other flammability fluids can be reduced according to the present invention. Flammable hydrofluoro, including, for example, ethylene oxide, HFC-152a, 1,1,1-trifluoroethane (HFC-143a), difluoromethane (HFC-32), propane, hexane, octane and the like Flammability associated with fluids such as carbon and hydrocarbons can be reduced according to the present invention. For the purposes of the present invention, a flammable fluid can be any fluid exhibiting a flammable range in air, as measured by any standard conventional test method such as ASTM E-681 or the like.

Any suitable amount of a compound or composition of the present invention may be added to reduce the flammability of the fluid according to the present invention. As known in the art, the amount added will depend at least in part on the degree of flammability of the subject fluid and to the extent that it is desirable to reduce the flammability thereof. In certain preferred embodiments, the amount of compound or composition added to the flammable fluid is effective to render the resulting fluid substantially inflammable.

Flame ( flame Suppression method

The present invention further provides a method of suppressing a flame, the method comprising contacting a fluid comprising a compound or composition of the invention with the flame. Any suitable method of contacting the flame with the composition of the present invention can be used. For example, the composition of the present invention may be sprayed or poured onto the flame, and at least some of the flame may be supported on the composition. In accordance with the teachings of the present invention, those skilled in the art will readily be able to apply various conventional devices and flame suppression methods used in the present invention.

Disinfection Method

In particular, most articles, devices and materials used in the medical field must be disinfected before use for reasons of health and safety, such as the health and safety of patients and hospital staff. The present invention comprises contacting an article, device or material to be disinfected with a compound or composition of the present invention comprising a composition of formula 1, preferably a composition of HFO-1234, and more preferably HFO-1234ze. Provide disinfection methods. While many known disinfectants are known to be suitable for use in conjunction with the present invention, disinfectants in the preferred embodiment are ethylene oxide (EO), formaldehyde, hydrogen peroxide, chlorine dioxide, ozone and compounds thereof. It includes. In this embodiment, ethylene oxide is the preferred disinfectant. In accordance with the teachings of the present invention, one skilled in the art will be able to determine the proportions of the disinfecting agents involved and the compounds of the invention used in combination with the disinfecting compositions and methods of the present invention, and further all such ranges It is included within the broad scope herein. Certain disinfection agents known to those skilled in the art, such as ethylene oxide, are relatively flammable compositions, and the compounds according to the invention are acceptable levels in the compositions of the invention, such as other compounds present in the composition in a quantitative manner. It is included in an amount effective to lower the flammability of the disinfectant composition.

Such a method may be a high temperature or low temperature disinfection method. In certain embodiments, the high temperature disinfection comprises exposing the article, device or material to be disinfected to a high temperature fluid comprising a compound or composition of the present invention at a temperature of about 250 to 270 ° F., preferably in a substantially sealed chamber. Include. In general, the process can be completed in less than about 2 hours. However, some articles, such as plastic articles and electrical components, cannot tolerate these high temperatures, so low temperature disinfection is required. For low temperature disinfection, the article to be sterilized is exposed to a fluid comprising the composition of the present invention at a temperature from room temperature to about 200 ° F, more preferably from room temperature to 100 ° F.

The pasteurization of the invention is a minimal two-step process carried out in a substantially sealed, preferably air tight, chamber. In a first step (sterilization step), the cleaned and stacked gas permeable bag is placed in the chamber. It is then evacuated and replaced with steam to evacuate the air from the chamber. In certain embodiments, it is desirable to inject steam into the chamber so that the relative humidity is preferably about 30 to 70%. This humidity can be introduced into the chamber after the desired relative humidity has been achieved to maximize the disinfection efficiency of the disinfectant. After sufficient time has passed for the disinfectant to penetrate the wrapping and reach the space of the article, the disinfectant and steam are discharged from the chamber.

In a second preferred step of the invention (aeration step), the article is vented to remove disinfection residue. Removal of such residues is particularly important in the case of toxic disinfectants, but is optional when substantially non-toxic compounds of the invention are used. Common aeration processes include air washes, continuous aeration, and mixtures thereof. Air wash is a batch process and generally involves degassing the chamber for a relatively short period of time, for example 12 minutes, and then introducing air into the chamber above atmospheric pressure. This cycle is repeated several hours until disinfectant removal is as desired. Generally, continuous venting involves drawing air through an inlet on one side of the chamber and then applying a slight vacuum to the outlet to draw it through the outlet on the other side of the chamber. In general, the two trials are combined. For example, a common attempt involves performing an aeration cycle after an air wash.

Example

The present invention will be described through the following examples, which are not intended to limit the present invention.

Example  One

Coefficient of Performance (COP) is a commonly used measure of refrigerant performance and is particularly useful for indicating the relative thermodynamic efficiency of a refrigerant in certain heating or cooling cycles involving evaporation or condensation of the refrigerant. In refrigerant engineering, this term refers to the ratio of useful refrigerant to energy applied by a compressor that compresses steam. The capacity of the refrigerant is an indication of the amount of cooling or heating that provides a measure of the miscibility of the compressor that pumps quantitative heat for the volume flow rate of a given refrigerant. That is, given a particular compressor, a refrigerant with a higher capacity will deliver higher cooling or heating capacity. Refrigerant COP measures under certain operating conditions result from the thermodynamic properties of the refrigerant using standard refrigerant circulation analysis techniques (see, for example, RC Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988). .

A refrigerant / air conditioning circulation system is provided with a condenser temperature of about 150 ° F and an evaporator temperature of about -35 ° F under compression of an isentropic line with a compressor inlet temperature of about 50 ° F. COP was measured for some compositions of the present invention over a range of condensation and evaporation temperatures and is shown in Table 1 below, based on HFC-134a with a COP value of 1.00, a volume value of 1.00, and an emission temperature of 175 ° F.

Refrigerant composition Relative COP Relative capacity Release temperature (℉) HFO 1225ye 1.02 0.76 158 HFO Trans-1234ze 1.04 0.70 165 HFO Sheath-1234ze 1.13 0.36 155 HFO 1234yf 0.98 1.10 168

This example shows that certain preferred compounds used with the compositions of the present invention each have better energy efficiency than HFC-134a (1.02, 1.04, and 1.13 compared to 1.00), and the compressor using the refrigerant composition of the present invention is discharged. Temperature will be generated (158, 165 and 155 compared to 175), and these results show that this is beneficial because the maintenance problem is reduced.

Example  2

Various cooling lubricants and the miscibility of HFO-1225ye and HFO-1234ze were tested. The lubricants tested were mineral oil (C3), alkylbenzenes (Zerol 150), ester oils (Mobil EAL 22 cc and Solest 120), polyalkylene glycol (PAG) oils (Goodwrench Refrigerantion Oil for 134a systems), and poly (alpha) -Olefin) oil (CP-6005-100). In the case of each refrigerant / oil mixture, the compounds of the invention were tested with adjustments of 5, 20 and 50% by weight of lubricant.

The lubricating composition is placed in a glass tube of heavy-walled. Each tube was degassed, the refrigerant compound according to the invention was added and the tube was then sealed. The tube was then placed in an air bath environmental chamber and the temperature was changed to a temperature of about -50 to 70 ° C. At intervals of about 10 ° C., it was visually observed that the contents of the tube were in one or more liquid phases. If more than one liquid phase is observed, the mixture is recorded as immiscible. If only one liquid phase is observed, the mixture is recorded as miscible. If two liquid phases are observed, one liquid phase occupies only a very small volume, but the mixture is recorded as partially miscible.

The polyalkylene glycol and ester oil lubricants were determined to be miscible within all ranges tested for all temperature ranges except for the polyalkylene glycol and HFO-1225ye mixtures, and the refrigerant mixture was between -50 and -30 ° C. It was immiscible with respect to the temperature range of and partially miscible with respect to the range of -20 to 50 ° C. At 60 ° C., at 50 wt% PAG in the refrigerant, the refrigerant / PAG mixture was miscible. At 70 ° C., 5% by weight of lubricant in the refrigerant and 50% by weight of lubricant in the refrigerant were miscible.

Example  3

The compatibility of the refrigerant compounds and compositions of the present invention with PAG lubricants in contact with the metals used in the cooling and air conditioning systems is tested at 350 ° C., which indicates very stringent in various cooling and air conditioning applications.

Aluminum, copper, and steel coupons are added to the heavy-wall glass tube. 2 grams of oil is added to the tube. The tube is then degassed and 1 gram of refrigerant is added. The tube was placed in an oven at 350 ° F. for 1 week and visually observed. At the end of the exposure period, the tube was removed.

This process was carried out on the following mixtures of oils and compounds of the invention:

a) HFC-1234ze and GM Goodwrench PAG oil

b) HFC-1243zf and GM Goodwrench oil PAG oil

c) HFC-1234ze and MOPAR-56 PAG oils

d) HFC-1243zf and MOPAR-56 PAG oil

e) HFC-1225ye and MOPAR-56 PAG oils

In all cases, there was minimal change in the appearance of the contents in the tube. The refrigerant compounds and compositions of the present invention were stable upon contact with aluminum, steel, and copper found in cooling and air conditioning systems, including compositions similar to lubricants and indicating that such compositions are used in this type of system.

Comparative example

Aluminum, copper and steel coupons were added to the heavy-wall glass tube with mineral oil and CFC-12 and heated at 350 ° C. for 1 week as in Example 3. At the end of the exposure, the tube was removed and visually observed. Liquid charges were observed in tum black, indicating that the charges in the tubes were severely degraded.

CFC-12 and mineral oils have been selected in a variety of refrigerant systems and methods. Accordingly, the refrigerant compounds and compositions of the present invention have a better substantial stability with the lubricants generally used than the refrigerant-lubricant mixtures widely used in the prior art.

Example  4

This example shows the use of a blowing agent according to one of the preferred embodiments of the present invention, namely the use of HFO-1234ze and the production of polyol foam according to the present invention. The compounds of the polyol foam formulas are prepared by the following table.

Polyol Ingredients * PBW Voranol 490 50 Voranol 391 50 water 0.5 B-8462 (Surfactant) 2.0 Polycat 8 0.3 Polycat 41 3.0 HFO-1234ze 35 Sum 140.8 Isocyanate M-20S 123.8 Index 1.10

* Voranol 490 is a polyol based on sucrose, Voranol 391 is a polyol based on toluene diamine, each available from Dow Chemical. B-8462 is available from Degussa-Goldschmidt. Polycat catalysts are based on tertiary amines and are available from Air Products. Isocyanate M-20S is a product of Bater LLC.

The foam was prepared by the first mixing of the components but no addition of blowing agent. The two Fisher-Porter tubes were each filled and sealed with about 52.6 g of a polyol mixture (without foaming agent), cooled in a refrigerator and formed a slight vacuum. Using a gas burette, about 17.4 grams of HFO-1234ze was added to each tube and the tubes were placed in warm water in an ultrasonic bath and held for 30 minutes. The resulting solution is cloudy and the vapor pressure reading at room temperature indicates a vapor pressure of about 70 psig, indicating that there is no blowing agent in the solution. The tubes are then placed in a freezer at 27 ° F. for 2 hours. Vapor pressure is measured again and found to be 14 psig. About 87.9 g of isocyanate mixture, placed in a metal container, is cooled to about 50 ° F. in a refrigerator. The polyol tubes are then opened and weighed into a metal mixing container (about 100 g of polyol blend is used). The isocyanate is then immediately poured into a polyol from the cooled metal container and mixed into an air mixer with a double propeller at 3000 RPM for 10 seconds. The blend immediately foams with stirring and is poured into a box of 8x8x4 inches and foamed. Because of the foam, the cream time cannot be measured. The foam has a gel time of 4 minutes and a tack free time of 5 minutes. The foam is then cured for 2 days at room temperature.

The foam was then cut into samples suitable for measuring physical properties and found to have a density of 2.14 pcf. K-factors were measured and shown as follows.

Temperature K, BTU In / Ft ² h ℉ 40 ℉ .1464 75 ℉ .1640 110 ℉ .1808

Example  5

This example illustrates the use of blowing agents according to two preferred embodiments of the present invention, namely HFO-1234ze and HFO-1234-yf, and the production of polystyrene foam. The experimental apparatus and design of the experiment were determined to be aided by the quality of the foam and whether a particular blowing agent and polymer could produce the foam. A blowing agent consisting of ground polymer (Dow Polystyrene 685D) and essentially HFO-1234ze is combined in the vessel. The sketch of the container is specified below. The vessel has a volume of 200 cm ³ and is made from two pipe flanges and a 2-inch diameter Schedule 40 stainless steel pipe 4-inch length (see Figure 1). The vessel is placed in an oven at a temperature of about 190 ° F. to about 285 ° F., preferably at 265 ° F. for polystyrene, and left until temperature equilibrium is reached.

The pressure in the vessel is then lowered and quickly produces foamed polymer. The blowing agent plasticizes the polymer as the polymer melts into it. The resulting densities of the two foams produced by this method are therefore shown in Table 1 and plotted in FIG. 1 by the density of foams produced using trans-HFO-1234ze and HFO-1234yf. The data show that foam polystyrene can be obtained by the present invention. The temperature of the die is about 250 ° F. for R1234ze with polystyrene.

Dow Polystyrene 685D Foam Density (lb / ft ³ ) Temperature (℉) trans-HFO-1234ze HFO-1234yf 275 55.15 260 22.14 14.27 250 7.28 24.17 240 16.93

Claims (45)

At least one fluoroalkene of formula (I)

Foam forming agent, comprising:
Wherein X is a C ₂ or C ₃ unsaturated, substituted or unsubstituted alkyl radical; Each R is independently Cl, F, Br, I or H; And z is 1-3.
The method of claim 1,
Wherein the at least one fluoroalkene is of formula (II)

Wherein R ′ is (CR ₂ ) _n Y, Y is CF ₃ , and n is 0 or 1;
The method according to claim 1 or 2,
Y is CF ₃ blowing agent for foam formation.
The method according to claim 1 or 2,
Y is CF ₃ , n is 0 and at least one of the remaining Rs is F.
5. The method according to any one of claims 1 to 4,
Wherein said at least one fluoroalkene comprises at least one tetrafluoropropene (HFO-1234).
The method of claim 5,
Wherein said at least one tetrafluoropropene comprises 1,3,3,3-tetrafluoropropene (HFO-1234ze).
The method of claim 6,
Wherein said at least one tetrafluoropropene comprises trans 1,3,3,3-tetrafluoropropene (trans HFO-1234ze).
The method according to claim 6 or 7,
Wherein said at least one tetrafluoropropene comprises cis 1,3,3,3-tetrafluoropropene (trans HFO-1234ze).
The method of claim 6,
Wherein said at least one tetrafluoropropene comprises 2,3,3,3-tetrafluoropropene (HFO-1234yf).
10. The method according to any one of claims 1 to 9,
At least about 5% by weight of at least one fluoroalkene of formula (I).
The method according to any one of claims 1 to 10,
Further comprising at least one additive selected from the group consisting of dispersants, cell stabilizers, surfactants, flame retardants, surfactants and combinations of two or more thereof.
The method according to any one of claims 1 to 11,
Difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), difluoroethane (HFC-152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,3,3, 3-hexafluoropropane (HFC-236fa), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc ), Water, CO ₂ and combinations thereof.
The method according to any one of claims 1 to 12,
Wherein the at least one fluoroalkene comprises a mixture of cis HFO-1234ze and trans HFO1234ze in a cis: trans weight ratio of about 1:99 to 10:99.
The method of claim 13,
Wherein the sheath: trans weight ratio is from about 1:99 to about 5:95.
15. The method according to any one of claims 1 to 14,
A foaming agent for foam formation having a Global Warming Index (GWP) of about 1000 or less, preferably about 500 or less, most preferably 150 or less.
A foam forming method comprising adding a blowing agent as defined in any one of claims 1 to 15 to a foamable composition capable of forming a foam.
A foaming composition comprising a blowing agent as defined in claim 1.
The method according to claim 16 or 17,
Wherein said at least one fluoroalkene comprises HFO-1234ze.
The method according to claim 16 or 17,
Wherein said at least one fluoroalkene comprises trans HFO-1234ze.
20. The method according to any one of claims 16 to 19,
The foaming composition further comprises at least one component selected from polyols, flame inhibitors, colorants, auxiliary blowing agents and combinations thereof, wherein the at least one component is added to the foam composition in a third stream to the mixing head or reaction site. A foam forming method or foam composition, which is added.
21. The method according to any one of claims 16 to 20,
The foam composition is a foam forming method or foam composition capable of forming a thermosetting foam.
The method of claim 21,
Wherein said thermoset foam is selected from polyurethane and / or polyisocyanurate foams.
21. The method according to any one of claims 16 to 20,
Wherein the foaming composition is capable of forming a thermoplastic foam.
The method of claim 23, wherein
Wherein said thermoplastic foam is selected from the group consisting of polystyrene, polyethylene, polypropylene and polyethylene terephthalate foam.
21. The method according to any one of claims 16 to 20,
Wherein the foam composition is capable of forming a closed cell, thermally insulating foam.
The method according to claim 16 or 17,
Wherein the blowing agent comprises HFO-1234ze, and the foaming composition is capable of forming a polyurethane and / or polyisocyanurate foam.
The method of claim 26,
Wherein the blowing agent comprises trans HFO-1234ze.
A foam formed from the method or composition of any one of claims 16-27.
The method of claim 28,
Foam, selected from blocks, slabs, laminates, pour-in-place panels, spray applied foams, foams, rigid foams, and combinations thereof.
a) a first component comprising a polyol or polyol mixture and a blowing agent as defined in any one of claims 1 to 15 and optionally a surfactant, a catalyst, a flame inhibitor and an isocyanate reactive component; And
b) a second component comprising isocyanurate and, optionally, a surfactant and an auxiliary blowing agent
Two-component pre-mix preparation for forming a polyurepan or polyisocyanurate foam, comprising.
At least one fluoroalkene of formula (I)

Propellant compositions comprising:
Wherein X is a C ₂ or C ₃ unsaturated, substituted or unsubstituted alkyl radical; Each R is independently Cl, F, Br, I or H; And z is 1-3.
32. The method of claim 31,
Further comprising at least one substance to be sprayed.
33. The method of claim 31 or 32,
Wherein the at least one fluoroalkene is of formula (II)

Wherein R is independently Cl, F, Br, I or H; R 'is (CR ₂ ) _n Y, Y is CF ₃ , and n is 0 or 1;
The method according to any one of claims 1 to 33,
Wherein said at least one fluoroalkene comprises 1,3,3,3-tetrafluoropropene (HFO-1234ze).
The method of claim 34, wherein
Wherein said at least one fluoroalkene comprises trans HFO-1234ze.
36. The method of claim 36 or 35,
Wherein said at least one fluoroalkene comprises cis HFO-1234ze.
The method of claim 34, wherein
A propellant composition comprising cis HFO-1234ze and trans HFO-1234ze in a cis: trans weight ratio of 1:99 to 10:99.
The method according to any one of claims 32 to 37,
The material to be sprayed is selected from cosmetic materials and medical materials.
The method of claim 38,
The material to be sprayed is a cosmetic material selected from deodorants, perfumes, hairsprays, cleansers and varnishes.
The method of claim 43,
The substance to be sprayed is a medical substance selected from anti-asthma, anti-oral drug, beta-antagonist and corticosteroid.
41. The method of any of claims 38-40.
Further comprising a solvent, a propellant composition.
The method according to any one of claims 31 to 41,
A propellant composition, in the form of an aerosol.
43. The method of claim 42,
Industrial aerosol articles selected from, for example, spray cleaners, lubricant sprays, contact cleaners and dusters; Personal care supplies; Home appliances; And propellant compositions in the form of automotive articles.
a) providing a propellant composition as defined in any of claims 1 to 15; And
b) propelling the substance or object
Comprising a method of propagating a substance or object.
The method of claim 44,
Wherein said at least one fluoroalkene comprises trans HFO-1234ze.

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